Process for the production of quaternary ammonium compounds



United States Patent PROCESS FOR PRGDUC'I'IQN OF QUATER- NARY ANEMGNIUM CGMPOUNDS Sydney H. Shapiro, Chicago, 111., assignor to Armour and Company, Chicago, Ill., a corporation of iiihiois Filed Oct. 16, 1957, Set. No. 699,355

8 Claims. (Cl. 26ii567.6)

This invention relates to an improved process for the production of quaternary ammonium compounds. In its preferred aspect, this invention relates to an improved process for the production of quaternary ammonium chlorides.

This application is a continuation-in-part of my pending application Serial No. 504,420, filed April 28, 1955, now abandoned.

The classic method for the production of quaternary ammonium compounds is the reaction between an amine and an alkylating agent, such as an alkyl halide. The reaction is usually carried out in a solvent medium, such as a low boiling alcohol, and under conditions of elevated temperature and pressure. When primary and secondary amines are employed, the reactions proceed according to the general equations:

It can be seen from the foregoing equations that one or two moles of acid are produced, depending upon the amine employed, for each mole of quaternary compound produced. This acid has a deleterious efiect upon the reaction, producing an amine salt with the unreacted amine and preventing further alkylation. Further, the acid also necessitates the use of special equipment to reduce corrosion. To obviate the difliculties attendant with the production of acid in the reaction, the method conventionally practiced is to add a quantity of alkali, usually sodium hydroxide because of its cost and availability, in excess of the stoichiometric amount needed to neutralize all of the acid formed during the reaction. The usual practice is to add all of the amine and all of the sodium hydroxide, along with the solvent, and then slowly add the alkylating agent by agitation until substantially all of the amine is converted to the desired quaternary ammonium compound. The pressure and temperature are maintained within the desired limits. When producing monoand di-long-chain aliphatic triand dimethyl quaternary ammonium chlorides commercially, the reaction generally requires about 16 to 24 hours and longer for completion.

While the sodium hydroxide substantially solved the problem of the acid produced in the reaction, there were also new problems created through its use. For example, one of the competing side reactions is the hydrolysis by the caustic of the alkylating agent to form an alcohol and a salt. Thus, the amount of alkylating agent necessary to convert all of the amine is considerably increased. One attempt at the solution of this problem involved the addition of the anhydrous caustic in increments of about 25% over the period of the reaction. However, this method proved ineiiectual since the loss of alkylating agent due to the venting of the reaction mixture to add the caustic resulted in as much loss of alkylating agent as through the effects of the deleterious hydrolysis.

In accordance with the present invention, I have provided a process for the production of quaternary ammonium compounds, essentially salt free, wherein sodium hydroxide is added, simultaneously with but separately from the alkylating agent, in a stoichiometrically proportional amount. The most surprising and advantageous aspect of my invention is the discovery that quaternary ammonium compounds can be produced from primary and secondary long-chain aliphatic amines in considerably less time than has heretofore been necessary. That is, whereas it took from 16 to 24 hours and longer to complete prior processes, mine can be completed in from about 2 to 6 hours, and even less. Further, there is no adverse effect upon the equality or quantity of the product produced, and the quantities of alkali and alkylating agent required are substantially diminished.

It is, therefore, an object of this invention to provide an improved process for the production of quaternary ammonium compounds.

Another object of this invention is to provide a process for the production of quarternary ammonium halides from primary and secondary amines.

Still another object of this invention is to provide an improved process for the production of long-chain aliphatic methyl quaternary ammonium chlorides from primary and secondary amines wherein sodium hydroxide is added simultaneously but separately from methyl chloride, in a stoichiometrically proportional amount.

A further object of this invention is to provide an improved process for the production of aliphatic quaternary ammonium chlorides from primary and secondary long chain aliphatic amines wherein there is added to the amine separately but simultaneously methyl chloride and a stoichiometrically proportional quantity of a. concentrated aqueous solution of sodium hydroxide.

Further and additional objects of this invention will become apparent from the specification and the drawing which illustrates, schematically, one embodiment of my process.

In general, my process involves injecting an alkylating agent and a stoichiometrically proportional quantity of sodium hydroxide separately but simultaneously into a reaction chamber containing an alcoholic solution of a long-chain aliphatic primary or secondary amine. This process results in a substantially complete conversion of the amine to a quarternary ammonium compound having only a very small quantity of soluble salt, and requires a much shorter period of time for reaction than possible by prior methods.

As the amine compounds, I can employ any long-chain aliphatic primary or secondary amine. Examples of the primary amines which I use include octyl amine, decyl amine, undecyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, octadecenyl amine, octadecadienyl amine, octadecatrienyl amine, and statistical mixtures of the foregoing amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of the mixed glycerides contained in vegetable and animal oils such as coconut oil, soybean oil, cottonseed oil, tallow, and the like. The preferred primary amines are the mixtures above described. The secondary amines which can be used include the secondary analogs of the aforementioned ali phatic primary amines, such as dioctylamine, didecyl amine, diundecyl amine, didodecyl amine, ditetradecyl amine, dihexadecyl amine, dioctadecyl amine, dioctadecenyl amine, dioctadecadienyl amine, dioctatrienyl amine, and the statistical mixtures of the foregoing amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of the mixed glycerides contained in vegetable and animal oils such as coconut oil, soybeam oil, cottonseed oil, tallow, and the like. The preferred secondary amines are 3 the mixtures described above. It should be noted that the long-chain aliphatic hydrocarbon radicals on the primary and secondary amines can be either saturated or unsaturated ,1 i employ as a solvent forthe amine and'as a medium for the reaction, a low-boiling alcohol, such as methanol, 7

soluble salt present in .the finalquaternary ammonium product. The alcohol is employedfingquantity suflici'ent 'to prepare the resulting, quaternary from the primary amines ,at an active concentration slightly in excess of 50%, and the quaternary. ammonium compounds from the secondary amines at an. active concentration slightly in excess of 75%. a a

-As the alkylating-agent, methyl chloride is preferably employed. Methyl chloride is gaseous at room temperature and liquid under pressure, and thus is easily adapted to a liquid injection system. Further, it is-readily available commercially. a

The alkaline material which I .preferto use in my process is sodium hydroxide by reason of its commercial availability and price, and also its high solubility at elevated temperatures when used as an aqueous solution.

net and stored in vessel 33, being heated when necessary for use by the circulation of steam through jacket 34.

The alkylating agent, methyl chloride, is pumped from storage tank 52 by means of pump 53 via line 54 through valves 55, 56 and 57 to reactor vessel 15. The rate of flow of methyl chloride to reactor 15 can be controlled by means of pilot valve 56 which is connected with ratio control 60, whichis in turn connected with caustic pump 44. Alternatively, a' ratio controller can be employed which is connected to two pilot valves, one in each of the lines 46 and 54 whose rates of flow are to be controlled. The ratio control 60 provides a proportioning of the quantities of methyl chloride and sodium hydroxide solution admitted into vessel 15. The amount of caustic solution supplied is stoichiometrically proportional to the quantity of methyl chloride entering the reaction vessel. Of course, the proportion of methyl chloride and sodium hydroxide solution will depend uponthe nature of the amine being converted to a quaternary.

That is, the conversion of a secondary amine requires proportionately less methyl chloride and sodium'hydroxide than for a primary amine. Similarly, the amount of salt produced as a contaminant is proportionately less.

The preferred limits on the aqueous concentration of the sodium hydroxide for producin a very minimum of dissolved salt in the final quaternary, viz., one percent or less, are from 68 up to about 73 weight percent. I prefer to use an aqueous solution containing between about 70 and about 72 weight percent. However, when the amount of soluble salt in the resulting-product is not'critical, aqueous concentrations as low as 50% can be employed. Solid anhydrous sodium hydroxide can also be employed in my process, preferably in a physical form which is net, is passed from alcohol storage tank 16 via line 17 through valves 20, 21 and 14 into reactor 15. Reactor 15 is provided with a jacket 22 through which either steam or cooling water may be passed. I acket 22 is provided with inlet line 23 and outlet line 24. The mixture of alcohol and amine are agitated by means of stirrer 25 driven by motor 26, and this agitation is continued throughout the entire reaction period. The temperature can be observed during the course of the reaction by means of a temperature recorder 31 connected with a thermo-couple 32 suitablymounted in the bottom of vessel 15. The

aqueous solution of caustic can be prepared in vessel 33' provided with the jacket 34 and a motor driven stirrer 35. Flake or stick caustic is added to vessel 33 through opening 36, water is added to the bottom of the tank via lines 40 and 41 through valves 42 and 43. Sufiicient caustic and water are added to prepare an aqueous solution having a concentration of from about 70 to about 72 Weight percent sodium hydroxide. The heat of solution of the sodium hydroxide helps considerably to raise the temperature of the resulting solution to the temperature of the amine. The hot aqueous solution is passed to vessel 15 from vessel 33 by means of pump 44 via lines 41, 45 and 46 through valves 43, 50 and 51. The lines are preferably steam traced and insulated to prevent solidification of the caustic in the line.

Alternatively, the concentrated aqueous solution of sodium hydroxide can be purchased as a commercial prod- During the course of the addition of methyl chloride,- cooling water is continuously circulated through jacket 22 of reactor vessel 15 to maintain the temperature of the reaction within the range of 160 to 250? F., preferably about 200 to 220 F. The pressure, as indicated by gauge 61, can vary between 0 and 75 pounds per square inch gauge, but is preferably maintained in the range of about 30 to about 60 pounds per square inch gauge. Higher pressures can be used but more expensive special equipment is necessary. The methyl chloride and stoichiometrically proportional amount of sodiuni hydroxide are added to the reaction mixture over a period of about 2 to about 6 hours, during which time the reaction mixture is continuously agitated. The reaction is considered complete when .the quantity of unre-. acted amine and amine hydrochloride in the reaction vessel is less than 2%., If after all the methyl, chloride has been added the reaction is still incomplete, the vaporized methyl chloride i the top of the reaction vesselcan be recirculated bymeans of pump 62 via line 63 through valves 64' and 65., This will increase and improvethe contacting of the methyl chloride with the unreacted amine, w. I

Upon completion of the reaction, the mixture contain: ing an aqueous alcoholic solution of quaternary, and dissolved and solid salt, is cooled to about to v F. and transferred via'line .70 through valve .71.-tofilter 72 which efiectsthe removal of the solid salt from the reactionmixture, After filtration the reactionmixture proceeds to dilutiontank 75 via line 73 through-valve 74 for adjustment of activity and pH, if necessary. Since the quaternaries are. purposely made ata higher concentration than ordinarily required, alcoholfnecessary, to obtain the desired activity can be used as a wash in a continuous pressure filter, thusobviating the need forfurther dilution. Therefore,when necessary, pH adjustment can be efiected in tank 75. The solution of quaternaryproceeds to storage tank 76 via line-77.

It will be appreciated that. the invention is not limited with respect to the apparatus or equipment described since the process can be .carriedout employing conventionalequipment. H

The following specific examples illustrate suitable modes of executing the invention. .It is .tobe understood that the examples are for illustrative .purposes'only and that the invention is not to. be regardedas unduly limited thereby. e H

- EXAMPLEI reaction Ivessel and heated toapproximatelyglQO" F.

Anneen 211T is at 5132 5 5621] mixture ofsecondary amines All? resulting from the hydrogenation of nitn'les produced by the ammoniation of acids resulting from the hydrolysis of tallow and contains approximately by weight 24% hexadecyl, 75% octadecyl and 1% octadecenyl radicals. A proportionating pump was set to deliver 0.356 gal. of 72 weight percent aqueous sodium hydroxide solution per gallon of methyl chloride. The methyl chloride and sodium hydroxide were added continuously but separately to the amine until the conversion to quaternary ammonium chloride was complete as indicated by a combined amine and amine hydrochloride content of less than 2%. The reaction was completed in about 3 hours and 150 gals. or 1,152 pounds of methyl chloride and 53.5 gals. or 754.4 pounds of sodium hydroxide were consumed in effecting the reaction. The theoretical quantitles of methyl chloride to convert 6,000 pounds of the secondary amine and sodium hydroxide to neutralize the acid formed in the conversion are 1,120 pounds and 625 pounds, respectively. The temperature employed was about 200 F. and the pressure range from to 65 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained about 1.79% free amine, soluble salt of about 0.3% and had an activity of 78.9%.

EXAMPLE II 6,250 pounds of Armeen 2C and 160 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to about 190 F. Armeen 2C is a statistical mixture of secondary amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of coconut oil and contains approximately 8% octyl, 9% decyl, 47% dodecyl, 18% tetradecyl, 8% hexadecyl and 10% octadecyl radicals. Methyl chloride and a 72 weight percent aqueous solution of sodium hydroxide were added continuously simultaneously but separately in approximate stoichiometric proportions with agitation to the alcoholic amine solution until the conversion to quaternary ammonium compound was complete as indicated by a combined amine and amine hydrochloride content of less than 2%. The reaction was complete in about hours and required 195 gals. of methyl chloride and 6 9.5 gals. of 72 weight percent sodium hydroxide solution. The theoretical quantities of methyl chloride to convert 6,250 pounds of the secondary amine and sodium hydroxide to neutralize the acid formed in the conversion are 191 gals. and 61 gals., respectively. The temperature during the reaction varied between about 200 and 250 F., and averaged about 210 F. The pressure during the reaction varied between 0 and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined secondary amine and amine hydrochloride, 0.18 weight percent soluble salt and had an activity of about 80%.

EXAMPLE 111 4,260 pounds or" Armeen TD and 439 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to about 190 F. Armeen TD is a statistical mixture of primary amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of tallow and contains approximately by Weight 2% tetradecyl, 24% hexadecyl, 28% octadecyl, and 46% octadecenyl radicals. Methyl chloride and a 72 weight percent aqueous solution of sodium hydroxide were added continuously simultaneously but separately in approximately stoichiometric proportions to the alcoholic amine solution until the conversion to quaternary ammonium compound was completed as indicated by a combined amine plus amine hydrochloride content of less than 2%. The reaction took place in about 6 hours and consumed 292 gals. of methyl chloride and 137 gals, of 72 weight percent aqueous solution of sodium hydroxide. The theoretical quantities of methyl chloride to convert 4,260 pounds of the primary amine and sodium hydroxide to neutrallze the acid formed in the conversion are 292 gals. and 126 gals, respectively. The temperature during the reaction varied between about 200250 F. and averaged about 210 F. The pressure during the reaction period varied between 0 and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined primary amine and amine hydrochloride, 0.4 weight percent soluble salt and had an activity of 58%.

EXAMPLE IV 6,250 pounds of Armeen 2HT and 200 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to a temperature of about 190 F. Armeen ZHT has the analysis composition given in Example I. Methyl chloride and 72 Weight percent aqueous sodium hydroxide solution were added simultaneously continuously but separately to the alcoholic amine solution in approximate stoichiometric proportions until the conversion to quaternary ammonium compound was complete as indicated by a combined amine plus amine hydrochloride content of less than 2%. The reaction took place in a period of about 3 hours and consumed gals. of methyl chloride and 53.5 gals. of sodium hydroxide solution. The theoretical quantities of methyl chloride to convert 6,250 pounds of the secondary amine and sodium hydroxide to neutralize the acid formed in the conversion are 155 gals. and 48.5 gals, respectively. The temperature during the reaction varied between about 200-250 F. and averaged about 210 F. The pressure during the reaction varied between 0 and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined secondary amine and amine hydrochloride, 0.1% soluble salt and had an activity of 82%.

EXAMPLE V 3,905 pounds of primary dodecyl amine and 450 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to a temperature of about F. Methyl chloride and 72% sodium hydroxide solution were added continuously simultaneously but separately in approximate stoichiometric proportions to the alcoholic amine solution until the conversion to quaternary ammonium compound was complete as indicated by a combined amine plus amine hydrochloride content of less than 2%. The reaction required 4 hours for completion and 400 gals. of methyl chloride and 174 gals. of aqueous sodium hydroxide solution were consumed in the conversion. The theoretical quantities of methyl chloride to convert 3,905 pounds of the primary amine and sodium hydroxide to neutralize the salt formed in the conversion are 400 gals. and 166 gals, respectively. The temperature during the reaction period varied between about 200-250 F. and averaged about 210 F. The pressure during the reaction period varied between 0 and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined primary amine and amine hydrochloride, 0.6% dissolved salt and had an activity of about 55%.

EXAMPLE VI 4,320 pounds Armeen S and 400 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to about 190 F. Armeen S is a statistical mixture of primary amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of cottonseed oil and contains approximately 20% hexadecyl, 17% octadecyl, 26% octadecenyl, and 37% octadecadienyl radicals. Methyl chloride and a 72 weight percent aqueous solution of sodium hydroxide were added continuously separately but in approximate stoichiometric proportions to the alcoholic no solution untilthe conversion to quaternary ammonium compound was complete as indicated'by a total amine plus amine hydrochloride content of less than 2%. The reaction was complete in a period of 6 hours and consumed 310 gals. of methyl chloride and 136 gals. of aqueous sodium hydroxide solution. The theoretical quantities of methyl chloride to convert 4,320 pounds of the primary amine and sodium hydroxide to neutralize the acidforrned in the conversion are 310 gals. and 128 gals, respectively. The temperature during the reaction period varied between 200-250" F. and averaged about 210 F. The pressure during the reaction period varied between about and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined primary amine and amine hydrochloride, 0.63% soluble salt and had'an activity of 57.5%.

EXAMPLE VII 4,320 pounds of Armeen TD and 400 gals of isopropyl alcohol were charged to a reaction vessel and the mixture heated to about 190 F. Armeen TD is a statistical mixture of primary amines having the analysis given in Example 111.. Methyl chloride and 72 weight percent aqueous sodium hydroxide were added continuously simultaneously but separately in approximate stoichiometric proportions to the alcoholic amine solution until the conversion to quaternary ammonium compound was a complete as indicated by a total amine plus amine hydrochloride content of less than 2%. The reaction was complete in 4 hours and consumed 310 gals. of methyl chloride and 136 galsof aqueous sodium hydroxide solution. The theoretical quantities of methyl chloride to convert 4,320 pounds of the primary amine and sodium hydroxide to neutralize the acid formed in the conversion are 310 gals. and 129 gals, respectively. The temperature during the reaction period varied between about 210-250 F. and averaged about 210 F. The pressure during the reaction period varied between 0 and 70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product containedless than 2% combined tallow amine and amine hydrochloride, 0.6% soluble salt and had an activity of 56%.

EXAMPLE VIII 4,320 pounds of Armeen CD and 500 gals. of isopropyl alcohol were charged to a reaction vessel and the mixture heated to about 190 F. Armeen CD is a statistical mixture of "primary amines resulting from the hydrogenation of nitriles produced by the ammoniation of acids resulting from the hydrolysis of coconut oil and contains approximately by weight 8% octyl, 9% decyl, 47% dodecyl, 18% tetradecyl, 8% hexadecyl, octadecyl, and 5% octadecenyl radicals. Methyl chloride and a 72% by weight aqueous sodium hydroxide solution wereadded continuously simultaneously but separately in approximate stoichiometricproportions to the alcoholic amine solution until the conversion to quaternary ammonium compound was complete as indicated by a combined amine plus amine hydrochloride content of less than 2%. The reaction was complete in 5 hours and consumed 410 gals. of methyl chloride and 180 gals. of aqueous sodium hydroxide solution. The'theoretical quantities. of methyl chloride to convert 4,320 pounds of the primary amine and sodium hydroxide to neutralize the acid formed in the conversion are 410 gals.'and 170 gals, respectively. The temperature during the reaction period varied between about 200-250" F. and averaged about 210 F. The pressure during the reaction varied between 0 and "70 pounds per square inch gauge and averaged about 40 pounds per square inch gauge. The resulting product contained less than 2% combined primary amine and amine hydrochloride, 0.6% soluble salt and had an activity of 56%. V

. The following are several examples-illustrating other methods for producing quaternary ammonium compoundsf" EXAMPLE IX .12,520 pounds of Armeen 25, '850 gals. of 99% isopropanol and 2,300 pounds of sodium bicarbonate were charged to a reactionvessel and the mixture heated to about 190 F. Armeen 2S is a statistical mixture of secondary amines resulting 'from the hydrogenation. of nitriles produced by the ammonia-don of acids resulting from the hydrolysis of cottonseed oil and contains approximately by weight 20% hexadecyl, 20% octadecyl, 25% octadecenyl, and 35% octadecadienyl radicals. Methyl chloride was continuously added to the reaction vessel 'until the conversion to quaternary ammonium compound was complete as indicated by a total amine plus amine hydrochloride content of less-than.2%. The reaction required over 32 hours for completion and 3,040'pounds of methyl chloride were consumed. The theoretical quantities of bicarbonate and methyl chloride required are 1,870 and 2,240 pounds, respectively. During the 32 hour operation the unit was cooled, vented and reheated six times to permit the excess pressure due to carbondioxide to be released, The temperature during the reaction period averaged about 210 F. and the pressure averagedabout pounds per square inch. (At this pressure the vessel had to be cooled and vented before more methyl chloride 'could be added.) The resulting product contained less than 2% combined amine and amine hydrochloride, 0.5% soluble salt and had an activity of 76%. a p 7 EXAMPLE X 12,420 .pdunds of Armeen 2HT, 885 gals. of 99% 'isopropanol and 2,300 pounds of sodium bicarbonate V were charged to a reaction vessel and the mixture heated to about F. Armeen 2HT is a statisticalmixture of secondary amines having the analysis set forth in Example 1. Methyl chloride was continuously added to the above reaction mixture until the conversion to quaternary ammonium compound was complete as indicated by a total amine and amine hydrochloride content of less than 2%.. The reaction required 28 hours for completion and consumed 3,360 pounds of methyl chloride. The theoretical amounts of bicarbonate and methyl chloride required for the conversion to quaternary ammonium chloride were 1,900 and 2,260 pounds, respectively. During this 28 hour operation the unit was cooled, vented and reheated five times to permit the excess pressure due to carbondioxide to be released. The temperature and pressure during the reaction period averaged 210 FQ 'and 90 pounds per square inch, respectively. (At this pressure the vessel had to be cooled and vented before more methyl chloride could be added.) The resulting productcontained less than 2% combined amine and amine hydrochloride, 0.5% soluble salt and had an activity of 75.2% V

, EXAMPLE XI 8,640 pounds of Armeen T, 850 pounds of flaked anhydrous sodium hydroxide and 1,550 gals. of 99% isopropanol were charged to a reaction vessel and the mixture heated to 190 F. Armeen T is a statistical mixture of primary amines resulting from the hydrogenation-of nitriles produced by the ammo'niation of acids resulting from the hydrolysis of tallow and contains approximately by weight 2% tetradecyl, 24% hexadecyl, 28% octadecyl, and 36% octadecenyl radicals. The conversion to quaternary ammonium compound was copsidered complete when the combined amine plus amine hydrochloride content was less than 2%. Methyl chloride was added to the abovemixture until the pH of the reaction approached '7. At this point the mixture was cooled and another 850 pounds of flaked caustic soda added. The above procedure was repeated until the reactionwas "complete. The operation required 40 hours and consumed 3,400 pounds of sodium hydroxide and 5,900 pounds of methyl chloride. The theoretical quantities of methyl chloride and sodium hydroxide required for the conversion of the primary amine to quaternary methyl ammonium chloride wherein methyl chloride is slowly added to a primary aliphatic hydrocarbon amine containing from 8 to 18 carbon atoms, the improvement which comprises adding simultaneously but separately ammonium compounds are 2,620 and 4,960 pounds, reliquid methyl chloride and a stoichiometrical ly proporspectively. The resulting product contained less than tional quantity of an aqueous solution contalning from 2% combined amine and amine hydrochloride, 1% soluabout 66 to 73 weight percent sodium hydroxide. ble salt and had an activity of 49.5%. 3. In a process for the production of a di-aliphatic dimethyl ammonium chloride wherein methyl chloride EXAMPLE XH is slowly added to a secondary aliphatic hydrocarbon 6,000 Pounds of Aimeen 750 Pounds of Sodium amine containing from 16 to 36 carbon atoms, the imhydroxide and 1,020 gals- Of 99% isopfopallol were provement which comprises adding simultaneously but charged to a reaction Vessel and the {niXtuIe heated to separately liquid methyl chloride and a stoichiometrically 190 F. Armeen C iS a Statistical mlXillrB of P y proportional quantity of an aqueous solution containing amines resulting from the hydrogenation 0t nitrrles profrom about 66 to 73 weight percent sodium hydroxide. duced by the ammoniation of acids resulting from the 4, A process for the production of a quaternary am hydrolysis of coconut oil and contains approximately by monium chloride which comprises adding an amine se- Weight 8% octyl, y y lected from the group consisting of primary and seconddecyl, 8% hexadecyl, 5% octadecyl, and 5% oct dew y ary amines having the formulas RNH and R NH wherein radicals. The conversion to quaternary ammomum com- 20 R is an aliphatic hydrocarbon radical having from 8 to pound was considered complete when the reaction In 1X- 18 carbon atoms to a reaction zone; adding with agitation ture contained less than 2% combined amine plus amrn over a period of at least two hours simultaneously but hydrochloride. Methyl chloride was added to the above separately methyl chloride and a stoichiometrically proreaction lTliXtllTe until the P 0f the Solution approached portional quantity of sodium hydroxide; and maintaining 7. At this point the IfiflCfiOIl was cooled, vented and the reaction mixture at a temperature in the range of an additional 750 pounds of caustic added. The con- 160 F. to 250 F. and a pressure of from 0 to 75 pounds version to quaternary ammonium compound required per square inch gauge. 38 hours and consumed 3,000 pounds of sodium hy- 5. A process for the production of an aliphatic tridroxide and 5,500 pounds of methyl chloride. The methyl ammonium chloride which comprises adding a theoretical quantities of sodium hydroxide and methyl 3 mixture of aprimary aliphatic hydrocarbon amine having chloride required for conversion to quaternary ammonium from 8 to 18 carbon atoms and a low boiling lower alkyl compound and neutralization of the acid formed are alcohol to a reaction zone; continuously adding with agita- 2,400 and 4,500 pounds, respectively. The resulting prodtion over a period of at least two hours simultaneously but uct contained less than 2% combined amine and amine separately liquid methyl chloride and a stoichiometrically hydrochloride, 1% salt and had an activity of 50.6%. proportional quantity of an aqueous solution containing Table I below summarizes the reaction times and quanfrom about 66 to 73 weight percent sodium hydroxide; tities of alkali and methyl chloride consumed in convertand maintaining the reaction mixture at a temperature I ing the various amines to quaternary ammonium comin the range of 160 F. to 250 F. and at a pressure of pounds as illustrated in the foregoing examples. It can from 0 to 75 pounds per square inch gauge. be readily seen from the data presented that the claimed 40 6. A process for the production of a di-aliphatic diprocess results in a considerable saving both in time and methyl ammonium chloride which comprises adding a material. mixture of a secondary aliphatic amine having 2 aliphat- Table I Percent Methyl Chloride Percent Example Alkali Hours Alkali Theory ver ver Reaction Actual Theory Theory Actual Theory 3.5 12 2.8 5.0 12 2 6.0 8.7 0 3.0 10.3 0 4.0 174.0 gals- 166.0 als--. 4.8 0 6.0 136.0 gals 128.0gals 5.9 0 4.0 136.0gals 129.0 gals 5.1 0 5.0 150.0 55215.... 5.9 0 32.0 lb 23.0 35 28.0 21.0 52 40.0 29.8 19 38.0 20.8 11

While this invention has been described and exemplified in terms of its preferred modifications, those skilled in the art will appreciate that variations may be made Without departing from the spirit and scope of the invention.

I claim:

1. In a process for the production of a quaternary ammonium chloride wherein methyl chloride is slowly added to an amine selected from the group consisting of primary and secondary amines having the formulas RNH and R NH wherein R is an aliphatic hydrocarbon radical having from 8 to 18 carbon atoms, the improvement which comprises adding simultaneously with but separate from said methyl chloride, a stoichiometrically proportional quantity of sodium hydroxide.

2. In a process for the production of an aliphatic triic hydrocarbon radicals containing from 8 to 18 carbon atoms and a low boiling lower alkyl alcohol to a reaction zone; continuously adding with agitation over a period of at least two hours simultaneously but separately liquid methyl chloride and a stoichiometrically proportional quantity of an aqueous solution containing from about 66 to 73 weight percent sodium hydroxide; and maintaining the reaction mixture at a temperature in the range of 160 F. to 250 F. and a pressure of from 0 to pounds per square inch gauge.

11 of an aqueoussolution containing about 72 weightpercent sodium hydroxide; maintaining the reaction mixture at a temperature inthe range of 160 F. to 220 F. and a pressure of about 30 to 60 pounds per square inch gauge; separating solid salt from the reaction mixture;

and recovering an alcoholic "solution of quaternary ammonium compound containing no more than one percent dissolved salt. u t

8. A process for the ,production ofiditallow dimethyl ammonium chloride which comprises adding a mixture of isopropyl alcohol and d-itallow amine to a reaction zone; continuously adding with agitation over a period of from 52 to 6 hours simultaneously but separately liquid methyl chloride and a stoichiometiically proportional quantity of an aqueous solution containing about 72 weight percent sodium hydroxide; maintaining the re- 1 2 action mixture at'a iemperanue-in t e masco o 160 F, to 220 :PL and a pressureof gaboutAfi to 60 w d r pe squa e. inch g ug aepa ti a sol as d m chloride :from the reaction mixture,- and recovering -;an alcoholic' solution Dfquaternary mp un contai ing :nomore than one-half percent dissolved salt.

ReferencesCit ed in the fil ei oflthispatent UNITED STATES PATENTS 2,212,149 Brubaker ct al. Aug. 20, 1940 2,316,625 Rothenberger Apr. 13, 1943 2,692,286 Stay'ner Oct. 19, 1954 OTHER REFERENCES Ralston et aL: J. Am. Chem. .Soc., "vol. 70 (1948), pages 977-78. V a i 

1. IN A PROCESS FOR THE PRODUCTION OF A QUATERNARY AMMONIUM CHLORIDE WHEREIN METHYL CHLORIDE IS SLOWLY ADDED TO AN AMINE SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINES HAVING THE FORMULAS RNH2 AND R2NH WHEREIN R IS AN ALIPHATIC HYDROCARBON RADICAL HAVING FROM 8 TO 18 CARBON ATOMS, THE IMPROVEMENT WHICH COMPRISES ADDING SIMULTANEOUSLY WITH BUT SEPARATE FROM SAID METHYL CHLORIDE, A STIOCHIOMETRICALLY PROPORTIONAL QUANTITY OF SODIUM HYDROXIDE. 